Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
  • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
  • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
  • C08F255/026—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms on to ethylene-vinylester copolymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
  • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
  • C08F279/04—Vinyl aromatic monomers and nitriles as the only monomers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
  • C08L23/08—Copolymers of ethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
  • C08L25/02—Homopolymers or copolymers of hydrocarbons
  • C08L25/04—Homopolymers or copolymers of styrene
  • C08L25/08—Copolymers of styrene
  • C08L25/12—Copolymers of styrene with unsaturated nitriles
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L53/005—Modified block copolymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
  • C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
  • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2207/00—Properties characterising the ingredient of the composition
  • C08L2207/04—Thermoplastic elastomer
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2207/00—Properties characterising the ingredient of the composition
  • C08L2207/53—Core-shell polymer
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
  • C08L23/08—Copolymers of ethene
  • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
  • C08L23/0869—Acids or derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
  • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers

Definitions

• the present invention relates to a thermoplastic resin composition, and more particularly to a thermoplastic resin composition comprising butadiene-based graft copolymer resin, acrylate-based graft copolymer resin, vinyl cyanide-aromatic vinyl-based copolymer resin and elastomer resin will be.
• ABS (Acrylonitrile-Butadiene-Styrene) resin is excellent in workability, moldability, impact resistance, strength and gloss, and is widely used in various electric, electronic and sundries parts.
• a part of the connection portion between the outer iron plate of the refrigerator and the inner resin molding is assembled into a table board, a lid, and a sash made by injection molding the resin.
• a urethane foam layer may be formed as an insulating material between the outer wall surfaces to give a heat insulating effect.
• blowing agent of the urethane foam layer examples include chlorofluorocarbon (CFC), hydrochlorofluorocarbon (HCF), and hydrofluorocarbon (HFC), but these are limited in use due to environmental problems.
• CFC chlorofluorocarbon
• HCF hydrochlorofluorocarbon
• HFC hydrofluorocarbon
• the present invention has been made to solve the problems of the prior art, excellent in chemical resistance to the blowing agent, excellent in environmental stress cracking resistance (ESCR), surface gloss and low temperature impact characteristics for refrigerators It is an object to provide a resin composition applicable to a thermoplastic molded part.
• Another object of the present invention is to provide a molded article produced using the resin composition.
• (A) Butadiene-based graft copolymer resin comprising 30 to 70% by weight of butadiene-based rubbery polymer core, and 30 to 70% by weight of graft shell comprising a vinyl cyanated monomer-derived unit and an aromatic vinyl monomer-derived unit. More than 30 parts by weight; (B) An acrylate graft copolymer comprising 30 wt% to 70 wt% of an acrylate rubbery polymer core, and 30 wt% to 70 wt% of a graft shell comprising a vinyl cyanated monomer-derived unit and an aromatic vinyl monomer-derived unit.
• the present invention provides a thermoplastic resin prepared using the resin composition, according to an embodiment.
• the resin composition according to an embodiment of the present invention is excellent in environmental stress cracking resistance (ESCR), in particular, excellent in chemical resistance and low temperature impact properties for the blowing agent, such as various electrical, electronic and sundries parts Can be applied.
• ESCR environmental stress cracking resistance
• the resin composition according to an embodiment of the present invention includes (A) 30% by weight to 70% by weight of a graft shell including 30% by weight to 70% by weight of a butadiene-based rubbery polymer core, a vinyl cyanated monomer-derived unit, and an aromatic vinyl monomer-derived unit.
• Butadiene-based graft copolymer resin containing 10 parts by weight or more and less than 30 parts by weight;
• An acrylate graft copolymer comprising 30 wt% to 70 wt% of an acrylate rubbery polymer core, and 30 wt% to 70 wt% of a graft shell comprising a vinyl cyanated monomer-derived unit and an aromatic vinyl monomer-derived unit.
• (E) 1 part by weight to 10 parts by weight of the polyester-based elastomer resin based on 100 parts by weight of the total resin of (A), (B) and (C).
• the resin composition according to an embodiment of the present invention is a butadiene-based graft copolymer resin, an acrylate-based graft copolymer and a vinyl cyanide-aromatic vinyl-based copolymer resin in a specific content range, in particular, ethylene-alkylacrylic
• ESCR environmental stress cracking resistance
• the butadiene-based graft copolymer resin is a vinyl cyanide monomer and an aromatic vinyl in the presence of 30% to 70% by weight, specifically 35% to 65% by weight of a butadiene rubbery polymer. 30 to 70% by weight of the mixture of monomers, specifically 35 to 65% by weight may be a copolymer resin graft copolymerized.
• the butadiene-based graft copolymer resin may be used by purchasing a commercially available one or by manufacturing.
• the vinyl cyanide monomer and the aromatic vinyl monomer may be graft copolymerized within 3 hours 30 minutes.
• the vinyl cyanated monomer may be included in the mixture of the vinyl cyanated monomer and the aromatic vinyl monomer in an amount of 20 wt% to 40 wt%, and specifically, may be included in an amount of 25 wt% to 35 wt%.
• a water-soluble initiator may be used in the polymerization reaction, an appropriate reaction temperature may be about 60 °C to 80 °C, specifically may be 65 °C to 80 °C.
• the butadiene-based rubbery polymer may be a rubbery polymer having an average particle diameter of 0.2 ⁇ m to 0.4 ⁇ m, specifically 0.25 ⁇ m to 0.35 ⁇ m.
• the average particle diameter of the butadiene-based rubbery polymer is smaller than the above range, impact strength and environmental stress crack resistance may be lowered. If the average particle diameter of the butadiene-based rubbery polymer is greater than the above range, the rubber production time may be longer and the gloss may be lowered.
• Butadiene-based rubbery polymers usable in accordance with one embodiment of the present invention include copolymers of polybutadiene, butadiene and monomers copolymerizable therewith (butadiene content in the copolymer is at least 50% by weight), copolymerized with butadiene
• Specific examples of the monomer that can be used include aromatic compounds such as styrene, ⁇ -methylstyrene and vinyltoluene, and vinyl cyanide compounds such as acrylonitrile and methacrylonitrile.
• the average particle diameter of the butadiene-based graft copolymer may be 0.2 ⁇ m to 0.4 ⁇ m, and specifically 0.25 ⁇ m to 0.35 ⁇ m.
• the average particle diameter of the butadiene-based graft copolymer satisfies the above range, it may exhibit appropriate impact strength, environmental stress crack resistance and vacuum forming, and may exhibit appropriate gloss.
• the butadiene-based graft copolymer resin (A) may be included in an amount of 10 parts by weight or more to less than 30 parts by weight based on 100 parts by weight of the total (A), (B) and (C) resin. It may be included in an amount of 15 parts by weight to 29 parts by weight, more specifically 20 parts by weight to 29 parts by weight. If the content of the butadiene-based graft copolymer resin satisfies the above range, it may exhibit environmental stress crack resistance of a predetermined level or higher required by the present invention, and may exhibit appropriate fluidity.
• the acrylate-based graft copolymer resin is vinyl cyanide in the presence of 30% to 70% by weight, specifically 35% to 65% by weight of the acrylate rubbery polymer. It may be a copolymer resin obtained by graft copolymerization of 30% to 70% by weight of the mixture of the monomer and the aromatic vinyl monomer, specifically 35% to 65% by weight.
• the acrylate-based graft copolymer resin is 30 wt% to 70 wt% of the acrylate rubbery polymer having an average particle diameter of 0.3 ⁇ m to 0.5 ⁇ m, specifically 0.35 ⁇ m to 0.5 ⁇ m, specifically 35 30% to 70% by weight of the mixture of the vinyl cyanated monomer and the aromatic vinyl monomer, specifically 35% to 65% by weight, is graft copolymerized in the presence of 1% by weight to 65% by weight, wherein the vinyl cyanated monomer in the mixture May be included in an amount of 20 wt% to 40 wt%, specifically 25 wt% to 35 wt%.
• the acrylate-based rubbery polymer is, for example, 0.1 to 4 parts by weight, specifically 0.1 to 3.5 parts by weight of the meta acrylate ester compound and 0.1 to 6 parts by weight, specifically 0.1 to 5 parts by weight It can be prepared by copolymerizing the negative vinyl cyanide monomer at the same time, the emulsifier 0.2 to 1.0 parts by weight of alkyl sulfo succinate metal salt having a carbon number of C12 ⁇ C18, alkyl sulfate ester or sulfonic acid metal salt having a carbon number of C12 ⁇ C20 We can use wealth.
• a rosin acid metal salt or a carboxylic acid metal salt having a carbon number of C12 to C20 may be used as an emulsifier.
• the acrylate rubbery polymer used in the present invention may include butyl acrylate, and examples of the methacrylic acid ester include ethyl methacrylate.
• Specific examples of the monomer copolymerizable with butyl acrylate include aromatic compounds such as styrene, ⁇ -methylstyrene and vinyltoluene, and vinyl cyanide compounds such as acrylonitrile and methacrylonitrile.
• the average particle diameter of the acrylate graft copolymer may be 0.3 ⁇ m to 0.5 ⁇ m, specifically 0.35 ⁇ m to 0.5 ⁇ m.
• the average particle diameter of the acrylate-based graft copolymer satisfies the above range, it may exhibit appropriate impact strength, environmental stress crack resistance and vacuum formability, and may exhibit appropriate gloss.
• the acrylate-based graft copolymer resin (B) is more than 5 parts by weight to less than 30 parts by weight based on 100 parts by weight of the total (A), (B) and (C) resin It may be included in an amount of, specifically, may be included in an amount of 6 to 20 parts by weight, more specifically 10 to 15 parts by weight. If the content of the acrylate-based graft copolymer resin is less than the above range, the environmental stress crack resistance may be reduced, it may not satisfy the crack resistance required by the present invention. In addition, when the content of the acrylate-based graft copolymer resin exceeds the above range, it may be difficult to give excellent vacuum forming due to the low molecular weight of the entire resin.
• the vinyl cyanide-aromatic vinyl copolymer resin (C) may be used alone, or may be used by mixing two or more kinds having different molecular weights.
• the vinyl cyanide-aromatic vinyl-based copolymer resin (C) contains (c1) 25 wt% to 40 wt% of vinyl cyanide compound, specifically 25 wt% to 38 wt% 20% to 30% by weight of vinyl cyanide-aromatic vinyl-based copolymer and (c2) vinyl cyanide compound having an average molecular weight of 50,000 g / mol to 150,000 g / mol, specifically 80,000 g / mol to 150,000 g / mol 1, selected from the group consisting of vinyl cyanide-aromatic vinyl-based copolymers containing 22 to 28% by weight and having a weight average molecular weight of 150,000 g / mol to 1,000,000 g / mol, specifically 150,000 g / mol to 900,000 g / mol. It may include more than one species.
• the vinyl cyanide-aromatic vinyl-based copolymer resin (C) may include 0 wt% to 100 wt% of the (c1) vinyl cyanide-aromatic vinyl copolymer, specifically 5 wt% to 95 wt%, (c2)
• the vinyl cyanide-aromatic vinyl copolymer may include 0 wt% to 100 wt%, specifically 5 wt% to 95 wt%.
• the weight average molecular weight of the vinyl cyanide-aromatic vinyl copolymer (c1) is less than the above range, environmental stress crack resistance may be lowered, and the weight average molecular weight of the vinyl cyanide-aromatic vinyl copolymer (c2) If it exceeds this range, there may be a problem that the melt viscosity is high and the processing is difficult and the appearance is degraded.
• the vinyl cyanide-aromatic vinyl-based copolymer (c1) 34 to 66% by weight, specifically 40 to 66% by weight and vinyl cyanide-aromatic vinyl-based copolymer (c2) 34 wt% to 66 wt%, specifically 40 wt% to 66 wt% may be used in combination.
• the vinyl cyanide-aromatic vinyl-based copolymer resin (C) of the present invention is 35 parts by weight to 65 parts by weight, specifically 40 parts by weight to 65 parts by weight based on 100 parts by weight of the total (A), (B) and (C) resins. It may be included in an amount by weight.
• the content of the vinyl cyanide-aromatic vinyl-based copolymer resin (C) is less than the above range, the fluidity may decrease, and when it exceeds the above range, the environmental stress cracking resistance may decrease.
• the resin composition according to an embodiment of the present invention may include an ethylene-alkyl acrylate copolymer elastomer resin to further improve environmental stress crack resistance.
• the ethylene-alkyl acrylate copolymer elastomer resin may improve the chemical resistance to the blowing agent, in particular Solstice ® blowing agent.
• the ethylene-alkyl acrylate copolymer elastomer resin may include an alkyl acrylate in an amount of 3% by weight to 30% by weight.
• the density of the ethylene-alkyl acrylate copolymer elastomer resin (ASTM D792) may be in the range of 0.900 g / cm 3 to 0.980 g / cm 3
• the melt index (ASTM D1238, 190, 2.16kg) is 0.5 g / 10 minutes to 50 g / 10 minutes, specifically 1 g / 10 minutes to 5 g / 10 minutes.
• (D) ethylene-alkyl acrylate copolymer resin is one selected from the group consisting of ethylene methyl acrylate copolymer, ethylene ethyl acrylate copolymer and ethylene butyl acrylate copolymer It may contain the above.
• Ethylene-alkyl acrylate copolymer elastomer resin according to an embodiment of the present invention is 1 to 10 parts by weight, specifically 2 based on 100 parts by weight of the total (A), (B) and (C) resin It may be included in an amount of 10 parts by weight to 10 parts by weight, more specifically 2.5 parts by weight to 6.5 parts by weight. If the ethylene-alkyl acrylate copolymer elastomer exceeds the above range surface gloss may be reduced, if less than the above range chemical resistance, environmental stress crack resistance and impact strength may be reduced.
• the resin composition according to an embodiment of the present invention may further include a polyester-based elastomer resin.
• the polyester-based elastomer resin may be a thermoplastic polymer in which (i) a crystalline hard segment and (ii) a soft segment are block copolymerized. (i) the crystalline hard segment and (ii) the soft segment may be random block copolymerized.
• the mixing ratio of the (i) crystalline hard segment and (ii) the soft segment may be 10:90 to 50:50, specifically 15:85 to 45:55 as a weight ratio. If the content of the crystalline hard segment is too small compared to the soft segment, the resin may be too difficult to use. If the content of the crystalline hard segment is too large compared to the soft segment, the resin may be rigid. There may be a process problem.
• the crystalline hard segment is an ester group formed by the condensation reaction of an aromatic dicarboxylic acid and its derivatives with an aliphatic diol, or an ester formed by the condensation reaction of an aromatic dicarboxylic acid with an aliphatic diol.
• Polyester compounds containing groups may be included as the main component.
• aromatic dicarboxylic acid examples include terephthalic acid (TPA), isophthalic acid (IPA), 2,6-naphthalenedicarboxylic acid (2,6-NDCA), 1,5-naphthalene dicarboxylic acid (1,5 -NDCA) or 1,4-cyclohexane dicarboxylic acid (1,4-CHDA), and the derivative of the aromatic dicarboxylic acid is an aromatic dicar substituted with a methyl group hydrogen of the -COOH group
• Carboxylate compounds such as dimethyl terephthalate (DMT), dimethyl isophthalate (DMI), 2,6-dimethyl naphthalene dicarboxylate (2,6-NDC), dimethyl 1,4-cyclohexanedicarboxylate (2 , 6-NDC), dimethyl 1,4-cyclohexanedicarboxylate (DMCD) or mixtures thereof.
• the derivative of the aromatic dicarboxylic acid may include DMT.
• the aromatic dicarboxylic acid and derivatives thereof may be used in an amount of 10 wt% to 55 wt%, specifically 15 wt% to 50 wt%, based on the total content of the polyester-based elastomer resin. If the aromatic dicarboxylic acid and its derivative are out of the range, the condensation copolymerization reaction may not proceed well because the overall condensation reaction balance is not balanced.
• an aliphatic diol compound having a molecular weight of 300 or less for example, ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol , 1,6-hexanediol and 1,4-cyclohexanedimethanol.
• One or more selected from the group consisting of, preferably 1,4-butanediol can be used.
• the aliphatic diol may be used in 10% by weight to 30% by weight, specifically 15% by weight to 25% by weight, based on the total content of the polyester-based elastomer resin, if the aliphatic diol compound is out of the range Condensation copolymerization reaction may not proceed well because the overall condensation reaction balance (balance).
• the (ii) soft segment may include a polyalkylene oxide compound including an ether group formed by an addition reaction as a main component.
• the polyalkylene oxide compound including the ether group may include an aliphatic polyether compound.
• polyether compounds include polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol (PTMEG), Polyoxyhexamethylene glycol, copolymers of ethylene oxide and propylene oxide, addition polymers of ethylene oxide and polypropylene oxide glycol, and copolymers of ethylene oxide and tetrahydrofuran, among which the number average molecular weight is in the range of 600 to 3,000. It is preferable to use PTMEG or polypropylene oxide glycol having a number average molecular weight of 2,000 to 3,000 capped with ethylene oxide.
• the hardness (Shore hardness D; shore D) of the (E) polyester-based elastomer resin may be determined by the amount of polyalkylene oxide included as a main component of the soft segment. That is, the polyalkylene oxide is used in about 40% to 80% by weight, specifically 45% to 80% by weight based on the total content of the polyester-based elastomer resin, if the polyalkylene oxide is less than the above range
• the condensation polymerization reaction may not proceed well due to the compatibility of hard segments and aliphatic polyether.
• the polyester-based elastomer resin may be prepared by primary melt condensation polymerization, or may be prepared in the form of a block copolymer of a high degree of polymerization having a lower melt index through secondary solid state polymerization.
• the polyester-based elastomer resin is an aromatic dicarboxylic acid and an aliphatic diol which is the main component of (i) the crystalline hard segment, starting material in the presence of titanium butoxide (TBT) as a catalyst, and (ii) a soft segment
• TBT titanium butoxide
• the main component polyalkylene oxide is subjected to transesterification for 120 minutes at a temperature of about 140 ° C. to 215 ° C. to produce a BHBT (Bis (4-hydroxy butyl) terephthalate) oligomer.
• BHBT Bis (4-hydroxy butyl) terephthalate
• TBT which is a catalyst
• TBT which is a catalyst
• TBT is reintroduced to the oligomer and subjected to a polycondensation reaction for about 120 minutes under a temperature condition of about 215 ° C to 245 ° C.
• the polycondensation reaction proceeds in a step of reducing the pressure from 760 Torr to 0.3 torr step by step.
• the polycondensation reaction is carried out melt polymerization until the desired flow index (MFI) in accordance with ASTM D-1238.
• MFI desired flow index
• the reactant is discharged in the reactor under nitrogen pressure to pellet the pellet through pelletizing.
• the melting point of the final polyester-based elastomer resin obtained by this process is 130 °C to 220 °C, preferably 140 °C to 210 °C, the melt index is 5 g / min to 30 g / min at 230 °C, 2.16Kg load Can be.
• the crystalline hard segment may include polybutyl terephthalate, and the soft segment may include polytetramethylene oxide glycol.
• Keyflex BT 2140D LG Chem
• keyflex BT 1172D having a hardness of 70D ( LG Chem Co., Ltd. can be used.
• the content of the mixture of the (E) polyester-based elastomer resin is 1 part by weight to 10 parts by weight based on 100 parts by weight of the total (A), (B) and (C) resin Parts, specifically 1.5 parts by weight to 9 parts by weight, and more specifically, may be used in an amount of 2 parts by weight to 6 parts by weight.
• the mixing weight ratio of (E) polyester-based elastomer resin and (D) ethylene-alkyl acrylate-based copolymer elastomer resin is 1: 1 to 1:10 weight ratio, specifically 1: It may be used in the range of 1 to 1: 5 weight ratio, more specifically 1: 1 to 1: 3.
• the ratio of the elastomer resin in the above range it can be excellent in environmental stress crack resistance, surface gloss and impact strength. If ethylene-alkyl acrylate copolymer resins are used less than the polyester-based elastomer resins, environmental stress cracking resistance and surface glossiness may decrease, which may be undesirable.
• the resin composition according to an embodiment of the present invention such as lubricants, lubricants, mold release agents, light and ultraviolet stabilizers, flame retardants, antistatic agents, colorants, fillers, impact modifiers, etc., as necessary without departing from the object of the present invention
• Other additives may be added and other resins or other rubber components may be used together.
• the thermoplastic resin manufactured by the resin composition according to the exemplary embodiment of the present invention may include a resin, a resin composition, or a composition of the resin composition included in the resin composition according to an example of the present invention. That is, the thermoplastic resin produced by the resin composition according to an embodiment of the present invention is a graphene comprising a (A) butadiene-based rubbery polymer core 30% to 70% by weight, a vinyl cyanated monomer-derived unit and an aromatic vinyl monomer-derived unit.
• thermoplastic resin prepared by the resin composition according to the embodiment of the present invention has a tensile strength (MD) of 380 to 450 measured according to ASTM D638 (50 mm / min), and the TE retention rate before and after the ESCR test ( MD) of 80% or more, TE retention rate (TD) of 50% or more before and after the ESCR test, 80% or more of surface gloss measured at an angle of 60 ° according to the method of ASTM D2457, and low temperature measured according to the ASTM D256 method.
• IZOD impact strength may be 15.0 kgf ⁇ cm / cm to 20 kgf ⁇ cm / cm.
• the present invention can provide a molded article manufactured using the resin composition according to an embodiment.
• the molded article is not particularly limited in the case of an article that can be made of plastic, and may be, for example, a display product, a mobile phone, a notebook, a housing such as a refrigerator, or various plastic parts.
• Solstice ® foaming agent since Solstice ® foaming agent has excellent chemical resistance and low temperature impact properties, it can be usefully used for extrusion sheet of refrigerator.
• the resin composition was prepared by mixing ethylene-alkyl acrylate copolymer elastomer resin (D) and polyester-based elastomer resin (E) in amounts of 4 parts by weight and 4 parts by weight, respectively, based on 100 parts by weight of the resin.
• the resin composition was melted and kneaded and extruded to prepare pellets.
• a resin composition and a specimen were obtained in the same manner as in Example 1, except that the resin composition was prepared in the contents and components shown in Table 1 below.
• a resin composition and a specimen were obtained in the same manner as in Example 1, except that the resin composition was prepared in the contents and components shown in Table 1 below.
• Extrusion sheet tensile strength (MD): Tensile strength at break was measured according to ASTM D638 (50 mm / min).
• ESCR Environmental stress crack resistance
• Izod (IZOD) impact strength (kgf ⁇ cm / cm): After putting the specimen in a -30 °C chamber for 20 hours, it was measured according to the ASTM D256 method. Specimen thickness was 1/4 ".
• Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Extrusion Sheet Tensile Strength (MD) 408 381 423 425 414 446 TE retention before and after ESCR test (MD) 100% 100% 92.1% 10.1 38.8 50.2 TE retention before and after ESCR test (TD) 61.8% 78.3% 60.3% 11.7 23.5 31.1 Surface gloss (60 °) 88.9% 89.1% 87.2% 90.3% 89.1% 89.3% Low temperature Izod impact strength (kgfcm / cm) 15.8 18.3 15.1 14.2 17.1 12.7 evaluation Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 Extrusion Sheet Tensile Strength (MD) 432 421 423 411 388 358 398 TE retention before and after ESCR test (MD) 10.8% 11.5% 15.1% 29.4% 100% 100% 100% TE retention before and after ESCR test (TD) 8.5% 9.4% 10.7%
• Comparative Examples 1 to 7 the TE retention before and after the ESCR test was not good in both the MD and TD directions, Comparative Example 8 was not good surface gloss, Comparative Examples 9 and 10, respectively, the extrusion sheet tensile strength and low temperature Izod's impact strength was not good.
• the acrylate-based graft copolymer (B) was not used (Comparative Example 2), or the acrylate-based graft copolymer (B) was insufficient.
• the acrylate-based graft copolymer (B) is used in an insufficient amount, and a polyester-based elastomer ( When E) was not used (Comparative Examples 4 and 5), the TE retention was not good before and after the ESCR test.

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• 2017
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